Light reflecting particles

ABSTRACT

Visible light reflecting particles comprise one or more detergent ingredients and a light reflecting component, which results in the particle having a specular visible light reflection which is greater in intensity than the specular visible light reflection of the ingredients per se. Preferably, the reflection is greater than the reflection of sodium citrate dihydrate, as defined herein. The reflecting particle preferably comprises the light reflecting component evenly applied on its surface. The particles are particularly suitable for incorporation into laundry or dish washing compositions, fabric conditioning compositions or hard-surface cleaning compositions.

TECHNICAL FIELD

The invention relates to visible light reflecting particles for use indetergent compositions, to processes for making the particles and todetergent compositions comprising the particles.

BACKGROUND TO THE INVENTION

In recent years, detergent manufacturers have introduced in theirproducts small amounts of dyed particles or speckles. The particles canmask de-coloration in the product and/or allows the incorporation in theproducts of small amounts of ingredients which do not have the colour ofthe bulk of the product by masking this colour difference. Furthermore,it has been found that the detergent users associate products havingdyed particles with improved cleaning that the consumer acceptance ofproduct comprising coloured particles is normally higher than productnot comprising such coloured particles.

These particles are often obtained by spraying-on an aqueous solution ofa specific dye onto hygroscopic material and addition of these materialsto the other ingredients, or directly onto the final detergent baseparticles and subsequently drying the thus dyed materials or particles.A problem associated with this method is that the hygroscopic materialabsorbs large amount of water which may result in caking of the product.This is particularly a problem when higher amounts of aqueousdye-solution need to be used, for example, when very diluted dyesolutions are to be used, or strongly dyed particles are needed or thedye is absorbed by the material or particles which are to be dyed.

Another problem associated with detergents comprising large amounts ofdye per particle can be that the dye can ‘bleed’ in the presence ofwater. This may be the case when the detergent is made by spraying onlarge amounts of aqueous dye solutions, or when the detergent compriseslarge amount of hygroscopic material or of course, when the detergentsare introduced to the washing or cleaning liquid, This ‘bleeding’ maycause colour changes of the product and the packing material. Moreover,under certain conditions, the dye or the dye particles which may depositon the fabrics, can ‘bleed’ on the fabrics and cause colour changes onthe washed fabric.

Also, those particles which cause decolouration and require masking tonot allows the presence of dye or sufficient amounts of dye.

However, despite these problems, it may be desirable to have some formof speckle particles present in the product to provide the requiredcontrast in the product and/or masking of certain ingredients in theproduct.

The inventor has now found an improved method of providing the requiredmasking of undesired coloration of detergent products. The inventor hasnow found that the same or a better masking or contrasting effect can beachieved when particles are incorporated in the product which reflectlight, which can be achieved by providing particles which comprise orconsist of a reflecting component. The presence of the specific lightreflecting component then produces a certain light reflection by theparticles containing the light reflecting component, which provides acontrast with the other ingredients of the products, or can mask theundesired colour of the particle containing the light reflectingcomponent or of other ingredients of the product, thus resulting in anoverall whiter or brighter product appearance. The light reflectingcomponent can generally be used in very small quantities to provide therequired effect

The use of the particles of the invention results in more formulationflexibility for the detergent manufacturer because the colour of theingredients to be used is now less important. Also, any, oftendifficult, process steps to provide detergent ingredients of therequired colour can now be dispensed of, for example one or morepurification steps.

The particles of the invention can be used in addition to any dyedspeckle, but they can also be used instead of any dyed speckleparticles. The present invention even allows reduction or elimination ofthe use of dyed particles and thus the problems associated therewith.Thus, since the particles of the invention are able to provide thecontrasting or masking when not coloured, these speckle particle may beuseful in certain products in countries where the use of dyes in suchproducts is not allowed.

SUMMARY OF THE INVENTION

The present invention provides a detergent particle comprising a visiblelight reflecting component and one or more particulate component whichcomprise one or more detergent ingredients, whereby the detergentparticle exhibits a specular visible light reflection which is of higherintensity than the specular visible light reflection of the particulatecomponent or components.

The reflecting detergent particles preferably has a lustre index,measured by a method described herein, which exceeds the lustre index ofsodium citrate dihydrate sample, whereof 100% of the particles has aparticle size of from 355 to 500 microns, having an mean particle sizeof 425 microns.

The reflecting particle preferably comprises the light reflectingcomponent evenly applied on its surface.

The particle is useful for incorporation in laundry or dish washingcompositions, fabric conditioning compositions or hard-surface cleaningcompositions. In particular , solid compositions are envisaged herein,but the particles may also be useful in liquid compositions which allowthe use of solid particles.

In another embodiment of the invention, a specific detergent compositionis provided which comprise s a reflecting particle consisting of thespecific light reflecting component.

Also provided are detergent tablets or bars comprising the reflectingcomponent, in particular on the surface of the tablet or bar.

The reflecting component can be introduced in the detergent product byseveral methods. The inventor however has also found specific methodswhich are particularly effective. Hereby, a common detergent ingredientor commonly used solvent, such as water, is used to incorporate thelight reflecting component into the detergent product. Thus, theinvention also relates to processes for making the compositions and theparticle and the use thereof.

DETAILED DESCRIPTION OF THE INVENTION

Visible Light Reflecting Particles

When used herein ‘reflecting’ or ‘light reflecting’ or ‘visible lightreflecting’ means specular visible light reflecting. For the purpose ofthe invention, when reference is made to specular visible lightreflection or the intensity thereof, this does not include diffuse lightreflection, which can also be understood from the definition of thelustre index below.

In one embodiment, the particle herein exhibits a specular visible lightreflection which is of higher intensity than the specular visible lightreflection of the particulate component, comprising one or moredetergent ingredients.

In another embodiment, a granular detergent composition or tablet isprovided which comprises one or more particulate detergent componentsand a particle consisting essentially of a visible light reflectingcomponent, whereby the particle exhibit a specular visible lightreflection which is of higher intensity than the specular visible lightreflection of the particulate component or each of the particulatecomponents.

Also provided is a detergent tablet or bar having a core containing oneor more particulate detergent components and a surface containing avisible light reflecting component, whereby the surface exhibit aspecular visible light reflection which is of higher intensity than thespecular visible light reflection of the particulate component or eachof the particulate components.

The detergent particles, compositions, tablets and bars of the inventioncan also be defined by a lustre index, which is characteristic for aspecific specular visible light reflection of the specific particle,composition, tablet or bar.

The lustre index is measured using a standard goniophotometric method.Incident visible light is directed at the product sample (e.g. thereflecting particle) at a given angle to the sample. This angle variesfrom 0° to 1 80° in increments. The intensity of visible light reflectedfrom the sample is then measured. Light which is reflected at the sameangle as the angle of the incident light is said to be specular. Lightreflected at all other angles is said to be diffuse. Lustre index isthus defined as the ratio of the specular reflected light to thediffusely reflected light.

Lustre index of a particle of the invention is defined relative to astandard, for example of the light reflecting component, prior toapplication or the particle, or relative to a chosen standard reflectingcomponent such as mica.

For example, a particle of the invention comprising a specular visiblelight reflecting component containing mica is compared with a sample ofthe mica not contained in the particle of the invention. For example asuitable standard sample is the commercially available Iriodin 183mica-based reflecting material (available form Merck), but also othermica based materials are suitable.

The standard and the product can then be measured by, for example,placing the mica standard and the particle containing the reflectingcomponent comprising the mica, in two separate, identical beakers anddirecting the visible light on the two samples in the two beakers, andmeasuring for each the light reflection under the given angle.

The lustre index can then be calculated with the formula:$\frac{\frac{L_{22.5,b}}{L_{22.5,s}} - \frac{L_{45,b}}{L_{0,s}}}{\frac{L_{22.5,b}}{L_{22.5,s}}} \times 100$

wherein L is the standard CIElab definition of whiteness intensity; 0,22.5 and 45 are the viewing angles in degrees for the goniophotometer,‘b’ refers to the L value of the product sample (e.g. the particle ofthe invention) for measurement and ‘s’ is the L value of referencestandard. Hence by this definition L_(22.5.b) is the whiteness intensityof the product sample measured at 22.5°. Similarly, L_(0.s) is thewhiteness intensity of the standard measured at 0°.

The lustre index of for example a detergent particle of the inventioncomprising a reflecting component comprising mica, is preferably from 3to 100, preferably from 5 to 100, or even from to 10 to 100, as measuredby the method above.

Preferably, when another reflecting component is used in the particle,composition, tablet or bar, the specular visible light reflectionthereof is of the same intensity as that of the particle, composition,tablet or bar, of the same composition but comprising instead areflecting component containing mica, which has a lustre index of 3 to100, preferably 5 to 100 or even 10 to 1000, as described above.

In a preferred embodiment the specular visible light reflection of theparticle of the invention, or of the detergent composition, bar ortablet of the invention is of higher intensity than the specular visiblelight reflection of sodium citrate salt sample having 100% by weight ofparticle between the particle size 355 and 600 and a mean particle sizeof 450 microns, as measured by use of sieving on American Standard wiresieves (ASTME 11:81), such that 100% of the particles is on sieve 42 and100% is through sieve 28.

Then, the particle, composition, tablet or bar of the inventionpreferably has a higher lustre index, compared to a mica standard as setout above, than the lustre index of said sodium citrate compared to thesame mica standard.

Preferably, the pigment component comprises a sheet layer material.Highly preferred is that the pigment component comprises BiOCl or evenmore preferably mica, or mixtures thereof. Preferred is mica asavailable from Merck under the name Iriodin. Iriodin 100-299 is a rangeof such mica-containing reflecting components for use herein, whereby183, 221, 223, 231 and 289 are examples of specific pigments within thisrange which are particularly suitable.

The light reflecting component preferably comprises also a metal oxide,such as TiO₂ or Fe₂O₃. The metal oxide is preferably applied onto thelight reflecting component or the particle as a coating. Highlypreferred light reflecting component herein comprises mica and TiO₂.

It may be preferred that the visible light reflecting componentcomprises water soluble or water-dispersable material. For example,where the material comprises water-dispersable material, the particlesize of the component will be such that at least 90% by weight,preferably at least 95% by weight or even 99% by weight is below 100microns or even 75 microns, preferably from 5 microns to 50 microns.

In one embodiment, the particle comprises one or more detergentingredients commonly employed in detergent compositions, as alsodescribed herein after, which are in particulate form. Then, the lightreflecting component is preferably applied onto the surface of thedetergent particle or part of the surface. Preferably, the lightreflecting component is applied evenly or homogeneously over the surfaceof the particle.

The reflecting detergent particle can for example comprise a particulateinorganic or organic salt or acid, such as a carbonate salt, sulphatesalt, phosphate salt, carboxylic acid or salt thereof. Hereby, it may bepreferred that the salt or acid is in crystalline form.

Highly preferred are citric acid or sodium citrate crystalline particlescomprising the light reflecting component.

Alternatively, the reflecting detergent particle may be comprise one ormore detergent actives, which are preferably selected from surfactants,builders, bleaching agents, enzymes, suds suppressors, softening agentsor mixtures thereof. In a preferred embodiment the light reflectingcomponent is applied to a detergent base granule, for example anagglomerate or spray dried or extruded detergent particle comprising oneor more of the detergent ingredients mentioned herein. It may bepreferred that the light reflecting component is applied to only thosedetergent particles which have an undesired colour, but it may also bepreferred that the light reflecting component is applied to thedetergent composition as a whole, comprising several particulatedetergent component.

Highly preferred may be that the particulate component is a base granuleformed by agglomerating or extruding a number of particulate components,such as blown powder particles, bleach activator particles, enzymeparticles, perfume particles, softening components, sudsuppressorparticles etc, preferably by using a binder (PEG, water, nonionicsurfactants are preferred), and that this base granule comprises thelight reflecting component on its surface.

In another embodiment the particle consist essentially of the lightreflecting component. Then, the light reflecting component is added ordry-mixed to the other detergent ingredients in particulate form. Thus,for example in a preferred embodiment particles consisting essentiallyof mica are added as reflecting particles to the detergent composition,to provide the required masking or contrasting.

In another embodiment of the invention the light reflecting component isapplied to the surface of a detergent tablet or detergent bar, or partof the surface thereof. Preferably, the light reflecting component isapplied such that it forms a homogeneous or even layer on the tablet orbar. For example, the tablet may comprise a conventional coating agentwhich comprises also the light reflecting component.

In addition to the light reflecting component on the surface of thetablet or bar, the tablet or bar may also comprise in its coreadditional light reflecting component, either in the form of detergentparticles containing the light reflecting component and/or as particlesconsisting of the light reflecting component.

The particle size of the reflecting particle can be any particle size,for example depending on the composition and the application of theparticle or the characteristics and application of the detergentcomposition comprising it.

The mean particle size of the light reflecting component will depend onwhich light reflecting component is used and on its application. Forexample, when the light reflecting component in applied to the surfaceof a detergent particle, the mean particle size of the light reflectingcomponent is preferably less than the mean particle size of thedetergent particle, whilst when the reflecting particle consistessentially of the light reflecting component, the mean particle size ofthe particle is not restricted by the mean particle size of the otherdetergent particles. For example, when the light reflecting componentcontains mica, it may be preferred that the mean particle size is around600 microns or less, because it has been found that larger particle sizesheet layer mica material can be too fragile and thus more difficult tohandle.

The preferred mean particle size of the light reflecting component ispreferably from 0.05 micron to 1500 micron, more preferably from 0.1micron to 1000 micron, but more preferably from 0.5 to 500 micron, oreven from 3 micron to 200 micron or most preferably from 5 micron to 50micron, preferably 90% or even 95% or even 99% by weight of thecomponent being from 5 to 100 or even to 50 microns, as described above.

Preferably, when the reflecting particle herein comprises one or moredetergent ingredients, the light reflecting component is present at alevel of from 0.001% to 15% by weight, more preferably from 0.01% to 7%by weight or even more preferably from 0.05% to 5% by weight of theparticle.

When the particle consist essentially of the light reflecting componentthe particle is preferably present in the composition at a level of from0.01% to 10%, more preferably from 0.05% to 5% or even form 0.01% to 3%by weight of the composition.

When the particle comprises one or more other detergent ingredients, theparticle can be made by a number of methods, including by any methodscommonly used to apply coating materials on detergent particles or tomix detergent ingredients.

A highly preferred method of the invention comprises the steps of

a) obtaining a particulate material which comprises the particulatecomponent or components including a binding material;

b) dusting the particulate material of step a) with the light reflectingcomponent;

c) optionally applying additional binding material onto the particle ofstep b).

The binding material may be part of the component or components or maybe specifically added to the component or components to provide theadhesion of the reflecting component. For example, the detergentcomponent can be a detergent base granule comprising nonionicsurfactant, capable of providing adhesion of the light reflectingcomponent, in which case no additional binding material may be needed.

Preferred is that the fight reflecting component becomes hereby evenlyor homogeneously applied an the surface of the particle detergentparticle.

Preferably, in step a) a binder material is applied on the detergentparticle, for example by spraying the binder material onto the particle.

Alternatively, or in addition thereto, the detergent particle maycomprise already one or more ingredients which provides the binding ofthe light reflecting component, for example, the detergent particle maycomprise a viscous ingredient such as a nonionic surfactant, whichprovides an adhesive effect for the light reflecting component. Then,the light reflecting component may even help to reduces the stickinessof the particle comprising the binder material, which may result in abetter flowability of the particles and may even reduce or eliminate theneed for other process aids normally used to improve the flowability ofdetergent particles, such as dusting with fine powdered material(aluminosilicates for example).

Another process for making the reflecting particle herein comprising thestep of applying onto a particulate detergent material, as describedabove, a mixture of the light reflecting component and a bindingmaterial. Any conventional coating process may be used therefor.

Yet another preferred process involves the step of wetting a particulatecomponent, for example with water or of a solution of other ingredientssuch as dyes in water, and then applying the reflecting component to theparticulate component, optionally followed by drying the thus obtainedparticle. This may be in particular preferred when organic or inorganicsalts or acids are coated with a reflecting component. Alternatively,the reflecting component can be dispersed or dissolved in a solvent,such as water, and then applied on a particulate component, optionallyfollowed by drying of the thus obtained particle.

The light reflecting component may also be mixed with the otherdetergent ingredients by any conventional granulation method, such asagglomeration, spray drying or extrusion, to form the reflectingparticle. However, this is a less preferred method, because only part ofthe light reflecting component will then be present on the surface ofthe particle. This is thus a less effective way of provide reflection bythe particles.

These processes can equally be use to apply the light reflectingcomponent onto a detergent tablet of bar, preferably evenly orhomogeneously over the surface of the tablet, or even in the form of acoating.

The binder may be any compound capable of providing adhesion of thelight reflecting component to the particle, or the tablet or bar.Preferably the binder material is a component which is viscous or can bemade into a viscous or liquid form by melting, or dissolution at theprocessing temperature. For example, water can be used to make asolution or dispersion of the reflecting component.

Preferably, the binder material is a detergent ingredient which has anadditional function in the composition, in addition to binding the lightreflecting component. Therefore, preferred binding materials are dyetransfer inhibiting polymers, soil releasing polymers, flocculating ordeflocculating agents, polymeric builders, such as polymericpolycarboxylates or polymeric polycarboxylic acids, which are describedherein after in more detail.

Highly preferred are binding materials comprising a nonionic surfactant,in particulate alkoxylated (preferably ethoxylated) nonionicsurfactants, but also wax and oils, and more preferably polyalkyleneglycols, most preferably polyethylene glycol, preferably having aaverage molecular weight of from 500 to 40,00, or even from 2000 to20,000 or even from 4000 to 10,000.

It may be highly preferred that the reflecting particle herein alsocomprises a colorant. The colorant may then be applied by any knownmethod for dyeing detergent particles. For example, the colorant may bemixed with the light reflecting component and preferably a bindermaterial and then applied onto the particle or tablet or bar.Alternatively, it may be preferred that the colorant is applied to theparticle comprising or consisting of the light reflecting component, forexample by spraying the colorant onto the particle with the lightreflecting component. Alternatively, if the particle comprises one ormore detergent ingredients, the colorant can be applied to the particleprior to application of the light reflecting component.

Highly preferred may be a reflecting particle comprising an organic orinorganic salt or acid comprising a colorant and a light reflectingcomponent, preferably a crystalline material such sodium citratecomprising preferably a blue or green dye and preferably mica,optionally also comprising TiO₂.

The colorant or dye used for dyeing the particles as used herein can bea dye stuff or an aqueous solution of a dye stuff or an non-aqueoussolution of or mixture with a dye stuff, for example using a carriermaterial such as a nonionic surfactant or other binder material. The useof an non-aqueous solution may have as an advantage herein that nosubsequent drying step is needed when the solution is applied to thespeckle particles. The dyestuff can be any suitable dyestuff. Specificexamples of suitable dyestuffs include E104—food yellow 13 (quinolineyellow), E110—food yellow 3 (sunset yellow FCF), E131—food blue 5(patent blue V), Ultra Marine blue (trade name), E133—food blue 2(brilliant blue FCF), E140—natual green 3 (chlorophyll andchlorphyllins), E141 and Pigment green 7 (chlorinated Cuphthalocyanine). Preferred dyestuffs may be Monastral Blue BV paste(trade name) and/or Pigmasol Green (trade name).

The particle herein may be coloured with a brightener, preferablycertain types of hydrophilic optical brighteners. The brightener speciesmay be any material known in the art, preferably those which arecommercially marketed under the tradename Tinopal by Ciba GeigyCorporation.

Compositions

The reflecting particle is preferably present in detergent compositions,preferably laundry or dish washing compositions, fabric conditioners, orhard surface cleaning compositions. In a preferred embodiment thecompositions are solid, preferably in the form of a granules, flakes,extrudates, bars or tablets. The compositions are preferably soliddetergents which have a density of at least 350 g/liter, more preferablyat least 500 g/liter.

The precise level of reflecting particles present in the compositiondepends in particulate on the degree of light reflection the reflectingparticle, the composition of the particle and the other ingredients ofthe composition, but also the particle size of the particles and theother ingredients of the composition, and the application of thecomposition.

The detergent composition, or the particle in one embodiment of theinvention, may comprise any conventional ingredient, commonly employedin detergent compositions, preferred ingredients described herein after.

The reflecting particle of the invention is particularly useful incompositions comprising ingredients which do not have the desiredproduct colour, or in compositions comprising hygroscopic ingredientswhich may absorb moisture and may cause any dye present, to bleed.

The compositions herein thus preferably comprising ingredients such asparticles comprising surfactant, enzymes, bleach activators, cellulosederivative or mixtures thereof, which tend to have an undesired colour.

The surfactant containing reflecting particles are preferablyagglomerates with anionic and/or nonionic surfactants, preferably withLAS and/or ethoxylated alcohol surfactants.

Also preferred are reflecting particles herein, containing peroxy acidbleach precursors, such as TAED, NAC-OBS, and other OBS-variants, ormixtures thereof.

The composition can be made by any method known in the art, including byagglomeration and/or spray-drying, whereby certain ingredients may beadmixed or sprayed-on as described herein. It may optionally bepreferred that the composition is made by mixing all or part of thegranules, including those made by agglomeration or spray-drying and eventhe reflecting particle of the invention, and subsequently adding abinder and agglomerating the mixture and binder to form agglomerateddetergent granules, which may be of the required particle size or whichmay be sieved to obtain particles of the required size.

It may be preferred that the composition comprises as builder system oras part of the builder system, an agglomerate particle, which maycomprise the light reflecting component, comprising from 0.5% to 80% byweight a crystalline layered silicate, from 10% to 70% by weight of asurfactant, preferably an anionic surfactant and preferably less than10% by weight of the agglomerate of free moisture, more preferably 30%to 60% by weight a crystalline layered silicate and 20% to 50% by weightof an anionic surfactant.

It may be highly preferred that the detergent composition comprises aneffervescence component, preferably comprising an acid source and analkali source capable of reacting together to form a gas upon contactwith water, in particular a carbon dioxide gas, formed by reaction of anorganic carboxylic acid and a carbonate source. It may be preferred thatthe effervescence component is a particulate component having an averageparticle size, by weight, of from 700 microns to 1400 microns,preferably from 750 microns to 1100 microns, preferably comprising anacid source and an alkali source.

It may be preferred that the effervescence component is substantiallyfree of water, preferably such that no water has been intimately mixedwith the effervescence component or part thereof, or that no water ispresent other than the moisture of the raw materials themselves.Typically, the level of water in intimate mixture with the effervescencecomponent is below 5% by weight of the total granule, preferably below3% and more preferably below 1.5%, preferably obtainable by dry-powdercompaction or pressure agglomeration.

This component may be in the form of a particle, which may be areflecting particle as described herein, comprising the light reflectingcomponent.

Suitable acids to be used herein include solid organic, mineral orinorganic acids, salts or derivatives thereof or a mixture thereof. Itmay be preferred that the acids are mono-, bi- or tri-protonic acids.Such acids include mono- or polycarboxylic acids preferably citric acid,adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid,tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid,malonic acid. Such acids are preferably used in their acidic forms, andit may be preferred that their anhydrous forms are used, or mixturesthereof. Derivatives also include ester of the acids.

The effervescence component or source preferably carbonate, bicarbonateor/and percarbonate salts, in particular bicarbonate and/or carbonate.Suitable carbonates to be used herein include carbonate and hydrogencarbonate of potassium, lithium, sodium, and the like amongst whichsodium and potassium carbonate are preferred. Suitable bicarbonates tobe used herein include any alkali metal salt of bicarbonate likelithium, sodium, potassium and the like, amongst which sodium andpotassium bicarbonate are preferred.

The effervescence component is preferably present in the compositionaccording to the present invention at a level of from 0.5% to 60% byweight, preferably from 2% to 50%, more preferably from 5% to 45% andpreferably such that the acid component is present at a level of from0.3% to 40%, more preferably from 1.0% to 35%, or even 2% to 25% or evento 15% by weight of the composition.

Surfactant

The compositions or in one embodiment preferably the particle herein,preferably contain one or more surfactants selected from anionic,nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactantsand mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Furtherexamples are given in “Surface Active Agents and Detergents” (Vol. I andII by Schwartz, Perry and Berch). A list of suitable cationicsurfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar.31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants aregenerally used in combination with one or more anionic and/or nonionicsurfactants.

Anionic Surfactant

The compositions or in one embodiment preferably the particle preferablycomprise an additional anionic surfactant. Essentially any anionicsurfactants useful for detersive purposes can be comprised in thedetergent composition. These can include salts (including, for example,sodium, potassium, ammonium, and substituted ammonium salts such asmono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate,carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonatesurfactants are preferred.

Highly preferred are surfactants systems comprising a sulfonate and asulfate surfactant, preferably a linear or branched alkyl benzenesulfonate and alkyl ethoxylsulfates, as described herein, preferablycombined with a cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucamine sulfates, and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beingdescribed herein).

Alkyl sulfate surfactants are preferably selected from the linear andbranched primary C₁₀-C₁₈ alkyl sulfates, more preferably the C₁₁-C₁₅branched chain alkyl sulfates and the C₁₂-C₁₄ linear chain alkylsulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₁₀-C₁₈ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁-C₁₈, mostpreferably C₁₁-C₁₅ alkyl sulfate which has been ethoxylated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and or sulfonate and alkyl ethoxysulfatesurfactants. Such mixtures have been disclosed in PCT Patent ApplicationNo. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅-C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂primary or secondary alkane sulfonates, C₆-C₂₄ olefin sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixturesthereof.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (‘alkyl carboxyls’), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy caaboxylates include those with the formulaRO(CH₂CH₂O)_(x) CH₂COO⁻M⁺ wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom O to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO—(CHR₁—CHR₂—O)—R₃ wherein R is a C₆ to C₁₈alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical,hydroxysuccinic acid radical, and mixtures thereof, and R₃ is selectedfrom the group consisting of hydrogen, substituted or unsubstitutedhydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl -1-octanoic acid and 2-pentyl-1-heptanoic acid. Certainsoaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R—CON (R¹) CH₂ COOM, wherein R is a C₅-C₁₇ linear or branchedalkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein.The nonionic surfactants are in particularly also useful as bindingmaterial or part thereof to apply the light reflecting component to theparticle or tablet or bars herein, as described above. The ethoxylatedand propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 molesof alcylene oxide, particularly ethylene oxide and/or propylene oxide,are suitable for use herein. The alkyl chain of the aliphatic alcoholcan either be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per moleof alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R²CONR¹Z wherein: R1 is H, Ch₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl,preferably straight-chain C₅-C₁₉ alkyl or alkenyl, more preferablystraight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydoxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.

Nonioinic Fatty Acid Amide Surfactant

Suitable fatty acid amide suractants include those having the formula:R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula:

R²O(C_(n)H_(2n)O)t(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀-C₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions in accord with the invention. These surfactants can bebroadly described as derivatives of secondary and tertiary amines,derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaterary phosphonium or tertiarysulfonium compounds. Betaine and sultaine surfactants are exemplaryzwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R′)₂N⁺R²COO—wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines areC₁₂₋₁₈ dimethyl-ammnonio hexanoate and the C₁₀₋₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent herein or inone embodiment preferably the particle include the quaternary ammoniumsurfactants. Preferably the quaternary ammonium surfactant is a monoC₆-C₁₆, preferably C₆-C₁₀ N-alkyl or alkenyl ammonium surfactantswherein the remaining N positions are substituted by methyl,hydroxyethyl or hydroxypropyl groups. Preferred are also themono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in thedetergent compositions or components thereof herein are cationic estersurfactants. The cationic ester surfactant is a, preferably waterdispersible, compound having surfactant properties comprising at leastone ester (i.e. —COO—) linkage and at least one cationically chargedgroup.

Suitable cationic ester surfactants, including choline estersurfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

In one preferred aspect the ester linkage and cationically charged groupare separated from each other in the surfactant molecule by a spacergroup consisting of a chain comprising at least three atoms (i.e. ofthree atoms chain length), preferably from three to eight atoms, morepreferably from three to five atoms, most preferably three atoms. Theatoms forming the spacer group chain are selected from the groupconsisting of carbon, nitrogen and oxygen atoms and any mixturesthereof, with the proviso that any nitrogen or oxygen atom in said chainconnects only with carbon atoms in the chain. Thus spacer groups having,for example, —O—O—(i.e. peroxide), —N—N—, and —N—O— linkages areexcluded, whilst spacer groups having, for example —CH₂—O—CH₂— and—CH₂—NH—CH₂— linkages are included. In a preferred aspect the spacergroup chain comprises only carbon atoms, most preferably the chain is ahydrocarbyl chain.

Cationic mono-alkoxylated Amine Surfactants

Highly preferred herein are cationic mono-alkoxylated amine surfactantpreferably of the general formula I:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 toabout 18 carbon atoms, preferably 6 to about 16 carbon atoms, mostpreferably from about 6 to about 14 carbon atoms; R² and R³ are eachindependently alkyl groups containing from one to about three carbonatoms, preferably methyl, most preferably both R² and R³ are methylgroups; R⁴ is selected from hydrogen (preferred), methyl and ethyl; X⁻is an anion such as chloride, bromide, methylsulfate, sulfate, or thelike, to provide electrical neutality; A is a alkoxy group, especially aethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably2 to about 15, most preferably 2 to about 8.

Preferably the ApR⁴ group in formula I has p=1 and is a hydroxyalkylgroup, having no greater than 6 carbon atoms whereby the —OH group isseparated from the quaternary ammonium nitrogen atom by no more than 3carbon atoms. Particularly preferred ApR⁴ groups are —CH₂CH₂OH,—CH₂CH₂CH₂OH, —CH₂CH(CH₃)OH and —CH(CH₃)CH₂OH, with —CH₂CH₂OH beingparticularly preferred. Preferred R¹ groups are linear alkyl groups.Linear R¹ groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants foruse herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, especiallyC₁₀-C₁₄ alkyl, preferably C₁₀ and C₁₂ alkyl, and X is any convenientanion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein theethoxy (CH₂CH₂O) units (EO) are replaced by butoxy, isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used indetergent compositions of the invention is preferably from 0.1% to 20%,more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% byweight of the composition.

Cationic Bis-alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the generalformula II:

wherein R¹ is an alkyl or alkenyl moiety containing from about 8 toabout 18 carbon atoms, preferably 10 to about 16 carbon atoms, mostpreferably from about 10 to about 14 carbon atoms; R² is an alkyl groupcontaining from one to three carbon atoms, preferably methyl; R³ and R⁴can vary independently and are selected from hydrogen (preferred),methyl and ethyl, X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, sufficient to provide electricalneutrality. A and A′ can vary independently and are each selected fromC₁-C₄ alkoxy, especially ethoxy, (i.e., —CH₂CH₂O—), propoxy, butoxy andmixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and qis from 1 to about 30, preferably 1 to about 4, and most preferably bothp and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for useherein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof preferably C₁₀,C₁₂, C₁₄ alkyl and mixtures thereof. X is any convenient anion toprovide charge balance, preferably chloride. With reference to thegeneral cationic bis-alkoxylated amine structure noted above, since in apreferred compound R¹ is derived from (coconut) C₁₂-C₁₄ alkyl fractionfatty acids, R² is methyl and ApR³ and A′qR⁴ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein includecompounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride orbromide.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu) isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

Perhydrate Bleaches

An preferred additional components of the compositions or in oneembodiment preferably the particle herein, is a perhydrate bleach, suchas metal perborates, metal percarbonates, particularly the sodium salts.Perborate can be mono or tetra hydrated. Sodium percarbonate has theformula corresponding to 2Na₂CO_(3.)3H₂O_(2,) and is availablecommercially as a crystalline solid.

The perhydrate bleach may be coated, for example with sulphate salts orcarbonate salts or silicate or mixtures thereof.

Potassium peroxymonopersulfate, sodium per is another optional inorganicperhydrate salt of use in the detergent compositions herein.

Bleach Activator

The composition or in one embodiment the particle herein, preferablycomprises a bleach activator, preferably comprising an organicperoxyacid bleach precursor. It may be preferred that the compositioncomprises at least two peroxy acid bleach precursors, preferably atleast one hydrophobic peroxyacid bleach precursor and at least onehydrophilic peroxy acid bleach precursor, as defined herein.

The bleach activator may also comprise a preformed peroxy acid bleach.

The production of the organic peroxyacid occurs by an in situ reactionof the precursor with a source of hydrogen peroxide.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogenperoxide in a perhydrolysis reaction to produce a peroxyacid. Generallyperoxyacid bleach precursors may be represented as

where L is a leaving group and X is essentially any functionality, suchthat on perhydroloysis the structure of the peroxyacid produced is

For the purpose of the invention, hydrophobic peroxyacid bleachprecursors produce a peroxy acid of the formula above wherein X is agroup comprising at least 6 carbon atoms and a hydrophilic peroxyacidbleach precursor produces a peroxyacid bleach of the formula abovewherein X is a group comprising 1 to 5 carbon atoms.

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 15% byweight, most preferably from 1.5% to 10% by weight of the detergentcompositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N— or O— acyl groups, which precursors can be selected from a widerange of classes. Suitable classes include anhydrides, esters, imides,lactams and acylated derivatives of imidazoles and oximes. Examples ofuseful materials within these classes are disclosed in GB-A-1586789.Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup. Any of R¹, R³ and R⁴ may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen,amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are —SO₃ ⁻M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺,—N⁺(R³)₄X⁻ and O<—N(R³)₃ and most preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁺wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, M is acation which provides solubility to the bleach activator and X is ananion which provides solubility to the bleach activator. Preferably, Mis an alkali metal, ammonium or substituted ammonium cation, with sodiumand potassium being most preferred, and X is a halide, hydroxide,methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N—,N,N¹N¹ tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred ashydrophilic peroxy acid bleach precursor.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and pentaacetyl glucose.

Amide Substituted Plkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitableherein, including those of the following general formulae:

wherein R¹ is an aryl or alkaryl group with from about 1 to about 14carbon atoms, R² is an alkylene, arylene, and alkarylene groupcontaining from about 1 to 14 carbon atoms, and R⁵ is H or an alkyl,aryl, or alkaryl group containing 1 to 10 carbon atoms and L can beessentially any leaving group. R¹ preferably contains from about 6 to 12carbon atoms. R² preferably contains from about 4 to 8 carbon atoms. R¹may be straight chain or branched alkyl, substituted aryl or alkylarylcontaining branching, substitution, or both and may be sourced fromeither synthetic sources or natural sources including for example,tallow fat. Analogous structural variations are permissible for R², R²can include alkyl, aryl, wherein said R² may also contain halogen,nitrogen, sulphur and other typical substituent groups or organiccompounds. R⁵ is preferably H or methyl. R¹ and R⁵ should not containmore than 18 carbon atoms total. Amide substituted bleach activatorcompounds of this type are described in EP-A0170386. It can be preferredthat R¹ and R⁵ forms together with the nitrogen and carbon atom a ringstructure.

Preferred examples of bleach precursors of this type include amidesubstituted peroxyacid precursor compounds selected from(6octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzene-sulfonate, and the highly preferred (6-nonanamidocaproyl)oxybenzene sulfonate, and mixtures thereof as described in EP-A -0170386.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid onperhydrolysis. Suitable O-acylated perbenzoic acid precursor compoundsinclude the substituted and unsubstituted benzoyl oxybenzene sulfonates,and the benzoylation products of sorbitol, glucose, and all saccharideswith benzoylatig agents, and those of the imide type including N-benzoylsuccinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substitutedureas. Suitable imidazole type perbennoic acid precursors includeN-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acylgroup-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preformed Organic Peroxyacid

The detergent composition may contain, in addition to, or as analternative to, an organic peroxyacid bleach precursor compound, apreformed organic peroxyacid , typically at a level of from 1% to 15% byweight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amidesubstituted compounds of the following general formulae:

wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbonatoms, R² is an alkylene, arylene, and alkarylene group containing from1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms. Amide substituted organic peroxyacidcompounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides,especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid anddiperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid are alsosuitable herein.

Heavy Metal Ion Sequestrant

The compositions of the invention or in one embodiment the particleherein preferably contain as an optional component a heavy metal ionsequestrant or chelant or chelating agent. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate) heavy metal ions. These components may also have calcium andmagnesium chelation capacity, but preferentially they show selectivityto binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to7.5% and most preferably from 0.3% to 2% by weight of the compositionsor component

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates.

Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylenephosphonate)hexamethylene diamine tetra (methylene phosphonate) andhydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acidand 1,1 hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenediamine disuccinic acid,ethylenediamine diglutaric acid, 2-hydroxypropylenediarnine disuccinicacid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

EP-A476,257 describes suitable amino based sequestrants. EP-A-510,331describes suitable sequestrants derived from collagen, keratin orcasein. EP-A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylicacid are alos suitable. Glycinamide-N,N′-disuccinic acid (GADS),ethylenediamine-N-N′-diglutaric acid (EDDG) and2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS) are alsosuitable.

Especially preferred are diethylenetriamine pentacetic acid,ethylenediamine-N,N′-disuccinic acid (EDDS) and 1,1 hydroxyethanediphosphonic acid or the alkali metal, alkaline earth metal, ammonium,or substituted ammonium salts thereof, or mixtures thereof

In particular the chelating agents comprising a amino or amine group canbe bleach-sensitive and are suitable in the compositions of theinvention.

Enzyme

Another highly preferred ingredient useful in the compositions herein orin one embodiment the particle herein is one or more enzymes.

Preferred additional enzymatic materials include the commerciallyavailable lipases, cutinases, amylases, neutral and alkaline proteases,cellulases, endolases, esterases, pectinases, lactases and peroxidasesconventionally incorporated into detergent compositions. Suitableenzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, and Esperaseby Novo Industries A/S (Denmark), those sold under the tradenameMaxatase, Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Protease enzyme may be incorporated into thecompositions in accordance with the invention at a level of from 0.0001%to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from aspecial strain of B licheniformis, described in more detail inGB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades,and those sold under the tradename Termamyl, Duramyl and BAN by NovoIndustries A/S. Highly preferred amylase enzymes maybe those describedin PCT/US 9703635, and in WO95/26397 and WO96/23873.

Amylase enzyme may be incorporated into the composition in accordancewith the invention at a level of from 0.0001% to 2% active enzyme byweight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, mostpreferably from 0.001% to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, forexample, from a lipase producing strain of Humicola sp., Thermomyces sp.or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomasfluorescens. Lipase from chemically or genetically modified mutants ofthese strains are also useful herein. A preferred lipase is derived fromPseudomonas pseudoalcaligenes, which is described in Granted EuropeanPatent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene fromHumicola lanuginosa and expressing the gene in Aspergillus oryza ashost, as described in European Patent Application, EP-A-0258 068, whichis commercially available from Novo Industri A/S, Bagsvaerd, Denmark,under the trade name Lipolase. This lipase is also described in U.S.Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Optical Brightener

The compositions herein or in one embodiment the particle herein mayoptionally contain from about 0.005% to 5% by weight of certain types ofhydrophilic optical brighteners, as mentioned above.

Photo-bleaching Agent

Photo-bleaching agents are preferred ingredients of the compositionsherein. Preferred photo-bleaching agent herein comprise a compoundshaving a porphin or porphyrin structure.

Porphin and porphyrin, in the literature, are used as synonyms, butconventionally porphin stands for the simplest porphyrin without anysubstituents; wherein porphyrin is a sub-class of porphin. Thereferences to porphin in this application will include porphyrin.

The porphin structures preferably comprise a metal element or cation,preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Sior Ga, or more preferably Al, most preferably Zn.

It can be preferred that the photo-bleaching compound or component issubstituted with substituents selected from alkyl groups such as methyl,ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl,pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

The photo-bleaching compound or component can have solubilizing groupsas substituents. Alternatively, or in addition hereto thephoto-bleaching agent can comprise a polymeric component capable ofsolubilizing the photo-bleaching compound, for example PVP, PVNP, PVI orco-polymers thereof or mixtures thereof.

Highly preferred photo-bleaching compounds are compounds having aphthalocyanine structure, which preferably have the metal elements orcations described above.

Metal phthalocyanines and their derivatives have the structure indicatedin FIG. 1 and/or FIG. 2, wherein the atom positions of thephthalocyanine structure are numbered conventionally.

The phthalocyanines can be substituted for example the phthalocyaninestructures which are substituted at one or more of the 1-4, 6, 8-11, 13,15-18, 20, 22-25, 27 atom positions.

Water-Soluble Builder Compound

The compositions in accord with the present invention or in oneembodiment the particle herein preferably contain a water-solublebuilder compound, typically present in detergent compositions at a levelof from 1% to 80% by weight, preferably from 10% to 60% by weight, mostpreferably from 15% to 40% by weight of the composition

The detergent compositions of the invention preferably comprisephosphate-containing builder material. Preferably present at a level offrom 0.5% to 60%, more preferably from 5% to 50%, more preferably from8% to 40.

The phosphate-containing builder material preferably comprisestetrasodium pyrophosphate or even more preferably anhydrous sodiumtripolyphosphate.

Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms, borates, and mixtures of any of theforegoing.

The carboxylate or polycarboxylate builder can be monomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid,tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates or their acids containing threecarboxy groups include, in particular, water-soluble citrates,aconitrates and citraconates as well as succinate derivatives such asthe carboxymethyloxy succinates described in British Patent No.1,379,241, lactoxysuccinates described in British Patent No. 1,389,732,and aminosuccinates described in Netherlands Application 7205873, andthe oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447. The mostpreferred polycarboxylic acid containing three carboxy groups is citricacid, preferably present at a level of from 0.1% to 15%, more preferablyfrom 0.5% to 8% by weight of the composition.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.Preferred polycarboxylates are hydroxycarboxylates containing up tothree carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acidor citrate/citric acid mixtures are also contemplated as useful buildercomponents.

Borate builders, as well as builders containing borate-forming materialsthat can produce borate under detergent storage or wash conditions areuseful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammonium pyrophosphate,sodium and potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The compositions in accord with the present invention or in oneembodiment the particle herein may contain a partially soluble orinsoluble builder compound, typically present in detergent compositionsat a level of from 0.5% to 60% by weight, preferably from 5% to 50% byweight, most preferably from 8% to 40% weight of the composition.

Examples of largely water insoluble builders include the sodiumaluminosilicates. As mentioned above, it may be preferred in onembodiment of the inevntion, that only small amounts of alumino silicatebuilder are present.

Suitable aluminosilicate zeolites have the unit cell formulaNa_(z)[(AlO₂)_(z)(SiO₂)y]. xH₂O wherein z and y are at least 6; themolar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferablyfrom 7.5 to 276, more preferably from 10 to 264. The aluminosilicatematerial are in hydrated form and are preferably crystalline, containingfrom 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formula:

Na₁₂[AlO₂)₁₂(SiO₂)₁₂]. xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆ [(AlO₂)₈₆(SiO₂)₁₀₆].276H₂O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. Thezeolite MAP can be present at a level of from 1% to 80%, more preferablyfrom 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as analkali metal alumino-silicate of the zeolite P type having a silicon toaluminium ratio not greater than 1.33, preferably within the range from0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminiumratio not greater than 1.15 and, more particularly, not greater than1.07.

In a preferred aspect the zeolite MAP detergent builder has a particlesize, expressed as a d₅₀ value of from 1.0 to 10.0 micrometers, morepreferably from 2.0 to 7.0 micrometers, most preferably from 2.5 to 5.0micrometers.

The d₅₀ value indicates that 50% by weight of the particles have adiameter smaller than that figure. The particle size may, in particularbe determined by conventional analytical techniques such as microscopicdetermination using a scanning electron microscope or by means of alaser granulometer. Other methods of establishing d₅₀ values aredisclosed in EP 384070A.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of thecompositions herein or in one embodiment the particle herein, and theymay also be present as or in the binder material to bind the lightreflecting component as described above, and they are preferably presentas components of any particulate components where they may act such asto bind the particulate component together. By organic polymericcompound it is meant herein essentially any polymeric organic compoundcommonly used as dispersants, and anti-redeposition and soil suspensionagents in detergent compositions, including any of the high molecularweight organic polymeric compounds described as clay flocculating agentsherein, including quaternised ethoxylated (poly) amine clay-soilremoval/anti-redeposition agent in accord with the invention.

Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.01% to 30%,preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weightof the compositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylates of MWt 1000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 2000 to100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-A-305282, EP-A-305283 andEP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having anaverage molecular weight of from 5,000 to 10,000, are also suitableherein.

Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such asmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluloseand hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cottonsoil release polymer according to U.S. Pat. No. 4,968,451, Scheibel etal., and U.S. Pat. No. 5,415,807, Gosselink et al., and in particularaccording to U.S. application Ser. No. 60/051517.

Another organic compound, which is a preferred claydispersant/anti-redeposition agent, for use herein, can be theethoxylated cationic monoamines and diamines of the formula:

wherein X is a nonionic group selected from the group consisting of H,C₁-C₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof,a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene,hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least16, with a typical range of from 20 to 35; for cationic diamines (b=1),n is at least about 12 with a typical range of from about 12 to about42.

Other dispersants/anti-redeposition agents for use herein are describedin EP-B-011965 and U.S. Pat. Nos. 4,659,802 and 4,664,848.

Suds Suppressing System

The detergent compositions of the invention or in one embodiment theparticle herein, when formulated for use in machine washingcompositions, may comprise a suds suppressing system present at a levelof from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from0.05% to 3% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term “silicone” as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises:

(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% byweight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycolrake copolymer with a polyoxyalkylene content of 72-78% and an ethyleneoxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level offrom 0.5% to 10%, preferably 1% to 10% by weight; a particularlypreferred silicone glycol rake copolymer of this type is DCO544,commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising aC₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to70%, by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Other highly preferred suds suppressing systems comprisepolydimethylsiloxane or mixtures of silicone, such aspolydimethylsiloxane, aluminosilicate and polycarboxylic polymers, suchas copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein or in one embodiment the particle herein mayalso comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weightof polymeric dye transfer inhibiting agents. They may also be present inor present as binding material to bind the light reflecting component,as described above.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-viylimidazole, polyvinylpyrrolidonepolymers or combinations thereof,whereby these polymers can be cross-linked polymers.

Polymeric Soil Release Agent

Polymeric soil release agents, herein after “SRA”, can optionally beemployed in the present compositions or reflecting particles. They mayalso be present in or present as binding material to bind the lightreflecting component, as described above.

If utilized, SRA's will generally comprise from 0.01% to 10.0%,typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, ofthe compositions.

Preferred SRA's typically have hydrophilic segments to hydrophiize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to be moreeasily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetranserification/oligomerization, often with a metal catalyst such as atitanium(IV) alkoxide. Such esters may be made using additional monomerscapable of being incorporated into the ester structure through one, two,three, four or more positions, without, of course, forming a denselycrossinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by:(a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in atwo-stage transesterification/oligomerization procedure; and (c)reacting the product of (b) with sodium metabisulfite in water. OtherSRA's include the nonionic end-capped 1,2-propylene/polyoxyethyleneterephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 toGosselink et al., for example those produced bytransesterification/oligomerization of poly(ethyleneglycol)methyl ether,DMT, PG and poly(ethyleneglycol) (“PEG”). Other examples of SRA'sinclude: the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol (“EG”), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, methyl (Me)-capped PEG andEG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al., the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT, optionally but preferably further comprising addedPEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C₁-C₄ alkyl celluloses and C₄ hydroxyalkylcelluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.;and the methyl cellulose ethers having an average degree of substitution(methyl) per anhydroglucose unit from about 1.6 to about 2.3 and asolution viscosity of from about 80 to about 120 centipoise measured at20° C. as a 2% aqueous solution. Such materials are available asMETOLOSE SM100 and METOLOSE SM200, which are the trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates usingdiisocyanate coupling agents to link polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al.; and (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst,the trimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.. Other classes include: (III) anionicterephthalate-based SRA's of the urethane-linked variety, see U.S. Pat.No. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes and filler salts, with sodium sulfatebeing a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% byweight of an organic acid, preferably citric acid. Also, preferablycombined with a carbonate salt, minor amounts (e.g., less than about 20%by weight) of neutralizing agents, buffering agents, phase regulants,hydrotropes, enzyme stabilizing agents, polyacids, suds regulants,opacifiers, anti-oxidants, bactericides can be present.

The tablets herein may comprise (additional) disintegrating agentsand/or (additional) coating agents, as preferred ingredients.

EXAMPLE I

The following reflecting particles are preferred reflecting particle ofthe invention. The particles 1 and 2 are made by spraying a solution ofthe dye in water onto the particulate component, then dusting the wettedcomponent with the reflecting component and the metal oxide, followed bydrying the particle in a fluidised bed.

The particles 3, 4 and 5 are prepared by first applying the bindermaterial onto the surface of the particular component, and subsequentlyapplying the pigment component and optionally applying the additionalbinder.

The levels in the table are in weight % of the reflecting particle.

Reflecting particle 1 2 3 4 5 particulate component sodium citratedihydrate 94 96.9 86 sodium carbonate 77 sodium sulphate 94 binder PEG1500 2 4 AE(5-15) 5 pigment component mica and TiO₂* 5 3 7 10 (weightratio typically 2:1 to 50:1) BiOCl and mica (weight 3.5 ratio 1:2)additional binder PEG 1500 1 AE(5-15) 5 dye 1 0.1 0.5 2 3 *Iriodin 183,221, 223, 231 or 289 as available form Merck; BiOCl as available fromMerck

Abbreviations used in the Granular Detergent Composition Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS Sodium linear C11-13 alkyl benzene sulfonate TAS Sodium tallow alkylsulfate CxyAS Sodium C1x-Cly alkyl sulfate C46SAS Sodium C14-C16secondary (2,3) alkyl sulfate CxyEzS Sodium C1x-C1y alkyl sulfatecondensed with z moles of ethylene oxide CxyEz C1x-C1y predominantlylinear primary alcohol condensed with an average of z moles of ethyleneoxide QAS R2.N + (CH3)2(C2H4OH) with R2 = C12-C14 QAS 1 R2.N +(CH3)2(C2H4OH) with R2 = C8-C11 APA C8-C10 amido propyl dimethyl amineSoap Sodium linear alkyl carboxylate derived from an 80/20 mixture oftallow and coconut fatty acids STS Sodium toluene sulphonate CFAAC12-C14 (coco) alkyl N-methyl glucamide TFAA C16-C18 alkyl N-methylglucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydroussodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite AHydrated sodium aluminosilicate of formula Na12(AlO2SiO2)12.27H2O havinga primary particle size in the range from 0.1 to 10 micrometers (weightexpressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate offormula δ-Na2Si2O5 Citric acid Anhydrous citric acid Borate Sodiumborate Carbonate Anydrous sodium carbonate with a particle size between200 μm and 900 μm Bicarbonate Anhydrous sodium bicarbonate with aparticle size distribution between 400 μm and 1200 μm Silicate Amorphoussodium silicate (SiO2:Na2O = 2.0:1) Sulfate Anhydrous sodium sulfate Mgsulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrateof activity 86.4% with a particle size distribution between 425 μm and850 μm MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecularweight about 70,000 MA/AA (1) Copolymer of 4:6 maleic/acrylic acid,average molecular weight about 10,000 AA Sodium polyacrylate polymer ofaverage molecular weight 4,500 CMC Sodium carboxymethyl celluloseCellulose ether Methyl cellulose ether with a degree of polymerizationof 650 available from Shin Etsu Chemicals Protease Proteolytic enzyme,having 3.3% by weight of active enzyme, sold by NOVO Industries A/Sunder the tradename Savinase Protease I Proteolytic enzyme, having 4% byweight of active enzyme, as described in WO 95/10591, sold by GenencorInt. Inc. Alcalase Proteolytic enzyme, having 5.3% by weight of activeenzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having0.23% by weight of active enzyme, sold by NOVO Industries A/S under thetradename Carezyme Amylase Amylolytic enzyme, having 1.6% by weight ofactive enzyme, sold by NOVO Industries A/S under the tradename Termamyl120T Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Lipolase Lipase (1)Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVOIndustries A/S under the tradename Lipolase Ultra Endolase Endoglucanaseenzyme, having 1.5% by weight of active enzyme, sold by NOVO IndustriesA/S PB4 Particle containing sodium perborate tetrahydrate of nominalformula NaBO2.3H2O, the particles having a weight average particle sizeof 950 microns, 85% particles having a particle size of from 850 micronsto 950 microns PB1 Particle containing anhydrous sodium perborate bleachof nominal formula NaBO2.H2O2, the particles having a weight averageparticle size of 800 microns, 85% particles having a particle size offrom 750 microns to 950 microns Percarbonate Particle containing sodiumpercarbonate of nominal formula 2Na2CO3.3H2O2, the particles having aweight average particle size of 850 microns, 95% particles having aparticle size of from 750 microns to 950 microns NOBS Particlecomprising nonanoyloxybenzene sulfonate in the form of the sodium salt,the particles having a weight average particle size of 750 microns to900 microns NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzenesulfonate, the particles having a weight average particle size of from825 microns to 875 microns TAED I Particle containingtetraacetylethylenediamine, the particles having a weight averageparticle size of from 700 microns to 1000 microns TAED IITetraacetylethylenediamine of a particle size from 150 microns to 600microns DTPA Diethylene triamine pentaacetic acid DTPMP Diethylenetriamine penta (methylene phosphonate), marketed by Monsanto under theTradename Dequest 2060 Photoactivated Sulfonated zinc phthlocyanineencapsulated in bleach (1) dextrin soluble polymer PhotoactivatedSulfonated alumino phthlocyanine encapsulated in bleach (2) dextrinsoluble polymer Brightener 1 Disodium 4,4′-bis(2-sulphostyryl)biphenylBrightener 2 Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2′disulfonate EDDS Ethylenediamine-N,N′-disuccinicacid, (S,S) isomer in the form of its sodium salt. HEDP1,1-hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with amolecular weight of x (typically 4,000) PEO Polyethylene oxide, with anaverage molecular weight of 50,000 TEPAE Tetraethylenepentaamineethoxylate PVI Polyvinyl imidosole, with an average molecular weight of20,000 PVP Polyvinylpyrolidone polymer, with an average molecular weightof 60,000 PVNO Polyvinylpyridine N-oxide polymer, with an averagemolecular weight of 50,000 PVPVI Copolymer of polyvinylpyrolidone andvinylimidazole, with an average molecular weight of 20,000 QEAbis((C2H5O)(C2H4O)n)(CH3)—N+—C6H12—N+—(CH3) bis((C2H5O)—(C2H4O))n,wherein n = from 20 to 30 SRP 1 Anionically end capped poly esters SRP 2Diethoxylated poly (1,2 propylene terephtalate) short block polymer PEIPolyethyleneimine with an average molecular weight of 1800 and anaverage ethoxylation degree of 7 ethyleneoxy residues per nitrogenSilicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foamcontroller to said dispersing agent of 10:1 to 100:1 Opacifier Waterbased monostyrene latex mixture, sold by BASF Aktiengesellschaft underthe tradename Lytron 621 Wax Paraffin wax Reflecting particle as made inexample I above Mica Iriodin 183, 221 or 223 as available form Merck

In the following examples all levels are quoted as % by weight of thecomposition:

TABLE I The following compositions are in accordance with the invention.A B C D E F G H I Spray-dried Granules LAS 10.0  10.0  15.0  5.0 5.010.0  — — — TAS — 1.0 — — — — MBAS — — 5.0 5.0 — — — C₄₅AS — — 1.0 2.02.0 — — — C₄₅AE₃S — — 1.0 — — — QAS 1.0 1.0 — — — DTPA, HEDP and/or 0.30.3 0.5 0.3 — — — EDDS MgSO4 0.5 0.5 0.1 — — — — Sodium citrate — — —3.0 5.0 — — — Sodium carbonate 10.0  7.0 15.0  10.0  — — — Sodiumsulphate 5.0 5.0 — — 5.0 3.0 — — — Sodium silicate 1.6R — — — — 2.0 — —— Zeolite A 16.0  18.0  20.0  20.0  — — — — — SKS-6 — — — 3.0 5.0 — — —— MA/AA or AA 1.0 2.0 11.0  — — 2.0 — — — PEG 4000 or 1500 5.0 2.0 — 1.0— 1.0 — — — QEA 1.0 — — — 1.0 — — — — Brightener  0.05  0.05  0.05 — 0.05 — — — — Silicone oil  0.01  0.01  0.01 — —  0.01 — — —Mica/TiO₂/PEG 4000 1.0 0.5  0.05 or 1500 (4:1:2) Agglomerate LAS — — — —2.0 2.0 — MBAS — — — — — — 1.0 C₄₅AS — — — — 2.0 — — AE₃ — — — — — 1.00.5 Carbonate — — 4.0 1.0 1.0 1.0 — Sodium citrate — — — — — — 5.0 CFAA— — — — — Citric acid — — — 4.0 — 1.0 1.0 QEA — — — 2.0 2.0 1.0 — SRP —— — 1.0 1.0 0.2 — Zeolite A — — — 15.0  26.0  15.0  16.0  Sodiumsilicate — — — — — — — PEG — — — — — — 4.0 — — Builder AgglomeratesSKS-6 6.0 — — — 6.0 3.0 — 7.0 10.0  LAS 4.0 5.0 — — 5.0 3.0 — 10.0 12.0  Dry-add particulate components Maleic 8.0 10.0  10.0  4.0 — 8.02.0 2.0 4.0 acid/carbonate/bicarbonate (40:20:40) QEA — — — 0.2 0.5 — —— — NACAOBS 3.0 — — 4.5 — — — 2.5 — NOBS 1.0 3.0 3.0 — — — — — 5.0 TAEDI 2.5 — — 1.5 2.5 6.5 — 1.5 — MBAS — — — 8.0 — — 8.0 — 4.0 LAS (flake)10.0  10.0  — — — — — 8.0 — Mica 0.3 — — — — — — — 0.5 Spray-onBrightener 0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 0.3 AE7 — — — — — 0.5 — 0.7 —Perfume 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 — Dry-add Citrate — — 20.0  4.0— 5.0 15.0  — 5.0 Percarbonate 15.0  3.0 6.0 10.0  — — 24.0  18.0  5.0Perborate — — — — 6.0 18.0  — — — Photobleach  0.02  0.02  0.02 0.1 0.05 — 0.3 — 0.03  Enzymes (cellulase, 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, lipase) Carbonate 0.0 10.0  — — — 5.0 8.010.0  5.0 Perfume (encapsulated) — 0.5 0.5 — 0.3 — 0.2 — — Sudssuppressor 1.0 0.6 0.3 — 0.10  0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5— — 0.3 — Citric acid — — — 6.0 6.0 — — — 5.0 Reflecting particle 1, 2,— — — 1.0 3.0 0.5 1.0 1.5 2.0 3, 4 or 5 SKS-6 — — — 4.0 — — — 6.0 —Fillers up to 100%

TABLE II The following compositions are in accordance with theinvention. A B C D E F G H I Spray-Dried Granules LAS 10.0  10.0  16.0 5.0 5.0 10.0  — — — TAS — 1.0 — — — — MBAS — — — 5.0 5.0 — — — C₄₅AS — —1.0 2.0 2.0 — — — C₄₅AE₃S — — — 1.0 — — — QAS — — 1.0 1.0 — — — DTPA,HEDP and/or 0.3 0.3 0.3 0.3 — — — EDDS MgSO4 0.5 0.4 0.1 — — — — Sodiumcitrate 10.0  12.0  17.0  3.0 5.0 — — — Sodium carbonate 15.0  8.0 15.0 10.0  — — — Sodium sulphate 5.0 5.0 — — 5.0 3.0 — — — Sodium silicate1.6R — — — — 2.0 — — — Zeolite A — — — 2.0 — — — — — SKS-6 — — — 3.0 5.0— — — — MA/AA or AA 1.0 2.0 10.0  — — 2.0 — — — PEG 4000 — 2.0 — 1.0 —1.0 — — — QEA 1.0 — — — 1.0 — — — — Brightener  0.05 0.05  0.05 —  0.05— — — — Silicone oil  0.01  0.01  0.01 — —  0.01 — — — Mica/TiO₂/PEG4000 2.0 1.0 0.2 0.5 2.0 0.1 — — — or 1500 (reflecting coating; 4:1:4)Agglomerate LAS — — — — — — 2.0 2.0 — MBAS — — — — — — — — 1.0 C₄₅AS — —— — — — 2.0 — — AE₃ — — — — — — — 1.0 0.5 Carbonate — — — — — 1.0 1.01.0 — Sodium citrate — — — — — — — — 5.0 CFAA — — — — — — — — — Citricacid — — — — — 4.0 — 1.0 1.0 QEA — — — — — 2.0 2.0 1.0 — SRP — — — — —1.0 1.0 0.2 — Zeolite A — — — — — 15.0  26.0  15.0  16.0  Sodiumsilicate — — — — — — — — — PEG — — — — — — 4.0 — — TAED 3.0 1.5 coatingMica/TiO₂/PEG 1500 — 1.5 0.6 3.0  0.05 (3:1:3) Builder Agglomerate SKS-66.0 5.0 — — 6.0 3.0 — 7.0 10.0  LAS 4.0 5.0 — — 5.0 3.0 — 10.0  12.0 Dry-add particulate components Maleic acid/ 8.0 10.0  4.0 4.0 — 8.0 2.02.0 4.0 carbonate/bicarbonate (40:20:40) QEA — — — 0.2 0.5 — — — —NACAOBS 3.0 — — 1.5 — — — 5.5 — NOBS/LOBS/DOBS — 3.0 3.0 — — — — — 5.0TAED I 2.5 — — 1.5 2.5 6.5 — 1.5 — MBAS — — — 8.0 — — 8.0 — 4.0 LAS(flake) — — — — — — — 8.0 — Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 — —0.6 — AE7 — — — — — 0.5 — 0.7 — Perfume — — — 0.8 — 0.5 0.8 0.5 1.0Dry-add Citrate 4.0 — 3.0 4.0 — 5.0 15.0  — 5.0 Percarbonate 15.0  3.06.0 10.0  — — 12.0  18.0  5.0 Perborate — — — — 6.0 18.0  — — —Photobleach  0.02  0.02  0.02 0.1  0.05 — 0.3 —  0.03 Enzymes(cellulase, 1.5 0.3 0.5 0.5 0.8 2.0 0.5  0.16 0.2 amylase, protease,lipase Carbonate — — — — — 5.0 8.0 10.0  5.0 Perfume (encapsulated) 0.60.5 0.5 — 0.3 0.5 0.2 0.1 0.6 Suds suppressor 1.0 0.6 0.3 —  0.10 0.51.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 — — 0.3 — Citric acid — — — 6.0 6.0— — — 5.0 SKS-6 — — — 4.0 — — — 6.0 — Reflecting particle 1, 2 1.0 2.0 —— 3.0 0.5 — — 1.0 or 3, 4 or 5 Fillers up to 100%

TABLE III The following is a composition the form of a tablet, bar,extrudate or granule in accord with the invention. Formulation H and Iare preferably in the form of an agglomerate of the individual detergentparticles or dry-added ingredient, agglomerate with PEG or waterrespectively, to obtain a granule of mean particle size between 500 and900 microns. A B C D E F G H I Sodium C₁₁-C₁₃ 12.0  16.0  23.0  19.0 18.0  20.0  16.0  5.0 6.0 alkylbenzenesulfonate Sodium C₁₄-C₁₅ alcohol4.5 — — — 4.0 6.0 5.0 sulfate C₁₄-C₁₅ alcohol ethoxylate — — — — — (0.5)sulfate C₁₄-C₁₅ alcohol ethoxylate (3) — — 2.0 — 1.0 1.0 1.0 sulfateSodium C₁₄-C₁₅ alcohol 2.0 2.0 — 1.3 — — 5.0 ethoxylate C₉-C₁₄ alkyldimethyl — — 1.0 0.5 2.0 0.5 0.5 hydroxy ethyl quaternary ammonium saltTallow fatty acid — — — — 1.0 Tallow alcohol ethoxylate — — — — — — —(50) Sodium tripolyphosphate/ 23.0  25.0  14.0  22.0  20.0  10.0  20.0 20.0  18.0  Zeolite Sodium carbonate 25.0  22.0  35.0  20.0  28.0  41.0 30.0  25.0  16.0  Sodium Polyacrylate (45%) 0.5 0.5 0.5 0.5 — — — Sodiumpolyacrylate/maleate — — 1.0 1.0 1.0 2.0 0.5 0.7 1.0 polymer Sodiumsilicate (1:6 ratio 3.0 6.0 9.0 8.0 9.0 6.0 8.0 0.5 — NaO/SiO₂)(46%)Sodium sulfate — — — — — 2.0 3.0 5.0 5.0 Sodium perborate/ 5.0 5.0 10.0 — 3.0 1.0 — 12.0  15.0  percarbonate Poly(ethyleneglycol), MW 1.5 1.51.0 1.0 — — 0.5 2.0 — ˜4000 (50%) Sodium carboxy methyl 1.0 1.0 1.0 —0.5 0.5 0.5 cellulose Citric acid or citric acid/ 5.0 2.0 6.0 — — 3.0 —7.0 5.5 carbonate/bicarbonate particle NOBS/NACA-OBS — 1.0 — — 1.0 0.7 —3.0 2.0 TAED 1.5 1.0 2.5 — 3.0 0.7 — 2.5 3.0 SRP 1.5 1.5 1.0 1.0 — 1.0 —0.2 0.5 Clay — — — 7.0 10.0  4.0 — — — Flocculating agent — — — 2.0 0.61.0 — Magnesium sulphate — — — — — 0.5 1.5 0.4 0.3 Chelant — — — — 0.80.6 1.0 0.8 0.5 Enzymes, including amylase, — — — — 2.0 1.5 2.0 1.0 1.0cellulase, protease and lipase Reflecting particle 1-5 — — — 1.0 — 3.0 —— — Mica/TiO₂/PEG 1500 coating 1.5 2.0 0.1 0.8 0.5 — 3.0 4.0 3.0 agent(10:1:20) Dyed speckle — — 0.5 — 0.5 — — 1.5 — soap QAS — — — 1.5 — —2.0 1.2 1.0 suds suppressor 2.5 3.0 NaSKS-6 3.5 5.0 minors, e.g.encapsulated 2.0 1.0 1.0 1.0 2.5 1.5 1.0 2.0 2.5 perfume, spray-onperfume, PVP, PVPVI/PVNO, brightener, encapsulated photo-bleach

TABLE V The following are compositions in the form of a tablet, bar,extrudate or granule in accord with the invention. A B C D SodiumC₁₁-C₁₃ 23.0  13.0  20.0  18.0  alkylbenzenesulfonate Sodium C₁₄-C₁₅alcohol — 4.0 — — sulfate Clay 5.0 — — — Wax 0.5 — — — C₁₄-C₁₅ alcoholethoxylate — — 2.0 sulfate Sodium C₁₄-C₁₅ alcohol 2.5 3.5 — — ethoxylate( C₉-C₁₄ alkyl dimethyl — — 0.5 hydroxy ethyl quaternary ammomium saltTallow fatty acid 0.5 — — — Tallow alcohol ethoxylate — — 1.3 (50)Sodium tripolyphosphate — 41.0  — 20.0  Zeolite A, hydrate (0.1-10 26.3 — 21.3  — micron size) Sodium carbonate 24.0  22.0  35.0  27.0  SodiumPolyacrylate (45%) 2.4 — 2.7 — Sodium polyacrylate/maleate — — 1.0 2.5polymer Sodium silicate (1.6 or 2 or 4.0 7.0 2.0 6.0 2.2 ratioNaO/SiO₂)(46%) Sodium sulfate — 6.0 2.0 — Sodium perborate/ 8.0 4.0 —12.0  percarbonate Poly(ethyleneglycol), MW 1.7 0.4 1.0 — ˜4000 (50%)Sodium carboxy methyl 1.0 — — 0.3 cellulose Reflecting particle 1, 2 or5 0.5 2.0 5.0 3.0 or mica/TiO₂ with PEG 1500 (5:1:20) Citric acid — —3.0 — NOBS/DOBS 1.2 — — 1.0 TAED 0.6 1.5 — 3.0 Perfume 0.5 1.0 0.3 0.4Soil release polymer — 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 Magnesiumsulphate — — — 1.0 Chelant — — — 0.5 speckle 1.0 — — — Enzymes,including amylase, — 1.0 — 1.5 cellulase, protease and lipase minors,e.g. brightener, 1.0 1.0 1.0 1.0 photo-bleach

What is claimed is:
 1. A granular detergent composition comprising oneor more granular detergent ingredients and a light reflecting particle,wherein the light reflecting particle comprises a particulate componentcomprising a metal salt and a light reflecting component comprising amixture of mica and TiO2 having a weight ratio of from about 2:1 toabout 50:1, or a mixture of BiOCl and mica at a weight ratio of about1:2; and further wherein the light reflecting particle exhibits aspecular visible light reflection which is of higher intensity than thespecular visible light reflection of the particulate component.
 2. Thecomposition according to claim 1, wherein the light reflecting particlehas a luster index exceeding the luster index of sodium citratedihydrate, further wherein the sodium citrate particles have a particlesize of from 335 microns to 600 microns and a mean particle size of 450microns.
 3. The composition according to claim 1, wherein theparticulate component is selected from the group consisting of sodiumcitrate dihydrate, sodium carbonate, sodium sulphate, and mixturesthereof.
 4. The composition according to claim 1, wherein the granulardetergent ingredient selected from surfactants, builders, bleachingagent, enzymes, suds suppressors, and mixtures thereof.
 5. Thecomposition according to claim 1, wherein the light reflecting particlefurther comprises crystalline sodium citrate, citric acid, or mixturesthereof.
 6. The composition according to claim 1 wherein the lightreflecting particle further comprises a colorant.
 7. The compositionaccording to claim 1 wherein the light reflecting particle furthercomprises a binder material.
 8. The composition according to claim 1wherein the binder material is selected from the group consisting ofnonionic surfactants, polyalkylene glycols, and mixtures thereof.
 9. Thecomposition according to claim 1, wherein the light reflecting particleis evenly applied on the surface of the detergent ingredient.
 10. Adetergent tablet or bar comprising the detergent particle of claim 1.11. A light reflecting particle comprising a particulate component and alight reflecting component, wherein the particulate component comprisinga metal salt; and the light reflecting component comprising a mixture ofmica and TiO2 having a weight ratio of from about 2:1 to about 50:1, ora mixture of BiOCl and mica at a weight ratio of about 1:2; and furtherwherein the light reflecting particle exhibits a specular visible lightreflection which is of higher intensity than the specular visible lightreflection of the particulate component.
 12. The particle according toclaim 11, wherein the light reflecting particle has a luster indexexceeding the luster index of sodium citrate dihydrate, further whereinthe sodium citrate particles have a particle size of from 335 microns to600 microns and a mean particle size of 450 microns.
 13. The particleaccording to claim 11, wherein the particulate component is selectedfrom the group consisting of sodium citrate dihydrate, sodium carbonate,sodium sulphate, and mixtures thereof.
 14. The particle according toclaim 11 wherein the light reflecting particle further comprisescrystalline sodium citrate, citric acid, or mixtures thereof.
 15. Theparticle according to claim 11 wherein the light reflecting particlefurther comprises a colorant.
 16. The particle according to claim 11wherein the light reflecting particle further comprises a bindermaterial.
 17. The particle according to claim 11 wherein the bindermaterial is selected from the group consisting of nonionic surfactants,polyalkyl ne glycols, and mixtures thereof.
 18. A detergent tablet orbar comprising a core comprising one or more particulate detergentingredient and a surface comprising the light reflecting particles ofclaim 11.